JPH0649043A - Azolylmethyl-fluorocyclopropyl derivative - Google Patents

Abstract

PURPOSE: To provide the new azolyl-fluorocyclopropyl derivatives having microbicidal, fungicidal properties.

CONSTITUTION: The compounds of the formula I (wherein R is the formulae II-VI), e.g. 1-(2-chlorophenyl)-2-(1-fluorocyclopropyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol, are obtained by allowing oxirane of the formula VII to react with 1,2,4-triazole of the formula VIII optionally in the presence of an acid-binding agent if suitable and a diluent. These compounds are suitable to prevent blast and sheath blight on gramineae and to prevent such diseases of grains as Leptosphaeria nodorum, leaf spot disease, net blotch, Pseudocercosporella herpotrichoides, Erysiphe and Fusariumculmorum.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

The present invention relates to new azolylmethyl-fluorocyclopropyl derivatives, a process for their preparation and their use as fungicides.

It has already been disclosed that certain azolylmethyl-cyclopropyl derivatives have fungicidal and fungicidal properties (EP-OS (European published specification) Nos. 0,2).
97,345). For example, 1- (4-chlorophenyl) -2- (1-fluorocyclopropyl) -3-
(1,2,4-triazol-1-yl) -propane-2
-All can be used to control fungi. The action of this material is good, but it sometimes leaves what is desired when used at low application rates.

Expression

[0004]

[Chemical 14]

[Wherein R is

[0006]

[Chemical 15]

## STR1 ## are found here as well as their acid addition salts and metal salt complexes.

The azolylmethyl-fluorocyclopropyl derivatives of formula (I) and their acid addition salts and metal salt complexes have the formula

[0009]

[Chemical 16]

Wherein R has the meaning given above
Oxirane of the formula, if appropriate in the presence of an acid binder and in the presence of a diluent.

[0011]

[Chemical 17]

Reacting with 1,2,4-triazole,
And, if appropriate, it has also been found to be obtained when the acid or metal salt is subsequently added over the resulting compound of formula (I).

Finally, it has been found that the new azolylmethyl-fluorocyclopropyl derivatives of formula (I) and their acid addition salts and metal salt complexes have very good fungicidal and fungicidal properties.

The substance according to the invention contains asymmetrically substituted carbon atoms. Therefore, they can be obtained in the form of optical isomers. The invention relates to the individual isomers as well as their mixtures.

Surprisingly, the substances according to the invention are the active substances of the most similar structure, 1- (4-chlorophenyl) -2- (1--, which have been known for a long time and have the same action. Fluoro-cyclopropyl) -3
-(1,2,4-triazol-1-yl) -propane-
It has better bactericidal and fungicidal properties than 2-ol. Preferred acid addition salts of the substances according to the invention are acid addition salts formed by adding the following acids onto the azolylmethyl-fluorocyclopropyl derivative of formula (I): hydrohalic acid, such as hydrochloric acid and Hydrobromic acid, especially hydrochloric acid, and also phosphoric acid, nitric acid, sulfuric acid, mono- and difunctional carboxylic acids and hydroxycarboxylic acids, such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid. And sulfonic acids such as p-toluenesulfonic acid, 1,5-naphthalenedisulfonic acid and camphorsulfonic acid, saccharin and thiosaccharin.

Preferred metal salt complexes of the substances according to the invention are main groups II to IV and subgroups I of the azolylmethyl-fluorocyclopropyl derivatives of the formula (I) and the periodic system of the elements.
To II and IV to VIII are addition products with salts of metals. Here, salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred. Suitable anions for these salts are acid-derived anions which lead to physiologically acceptable addition products. Particularly preferred acids of this type are, in this context, hydrohalic acids, such as hydrochloric acid and hydrobromic acid, and also phosphoric acid,
Nitric acid and sulfuric acid.

2- (2-chlorobenzyl) -2- (1-
When fluoro-cyclopentyl) -oxirane is used as the starting material and 1,2,4-triazole as the reactant, the course of the process according to the invention can be illustrated by the following formula:

[0018]

[Chemical 18]

The oxirane of formula (II) required as starting material in the process according to the invention has hitherto not been known. Those are the expressions

[0020]

[Chemical 19]

[Wherein R has the meaning described above]
Benzyl ketone of α) formula in the presence of a diluent

[0022]

[Chemical 20]

Dimethyloxosulfonium methylide,
Or β) formula

[0024]

[Chemical 21]

It can be produced by reacting with either dimethylsulfonium methylide.

The benzyl ketone of formula (IV) has the formula a) in the first step:

[0027]

Embedded image Benzyl chloride of R—CH ₂ Cl (VII), where R has the meanings given above, is added with a diluent such as ethylene glycol at a temperature of 50 ° C. to 150 ° C. under a protective gas atmosphere. Reacting with excess zinc powder in the presence of dimethyl ether to remove excess zinc powder and then b) in the second step, the formula

[0028]

Embedded image The resulting benzyl derivative of R—CH ₂ ZnCl (VIII), where R has the meanings given above, is treated with a palladium catalyst such as bis- (tri) at a temperature of 20 ° C. to 100 ° C. Formula in the presence of phenyl-phosphine) -palladium (II) chloride and in the presence of a diluent such as ethylene glycol dimethyl ether.

[0029]

[Chemical formula 24]

It can be produced by reacting with 1-fluoro-cyclopropane-carboxylic acid chloride.

The compounds of the formulas (VII) and (IX) can be prepared by methods which are known or known in principle (EP-OS (European publication specification) Nos. 0,436. 348 and EP-OS (European published specification) 0,461,483).

The dimethyloxosulfonium methylides of the formula (V) required as reactants for carrying out the process variant (α) for the preparation of the oxiranes of the formula (II) are known (J Am. Chem. Soc. 87 ,
1363-1364 (1965)). In the above reaction, trimethyloxosulfonium iodide was treated with sodium or sodium amide, especially potassium tert. Treating it as freshly prepared by reacting with butyrate or sodium methylate or by preparing it in situ by reacting trimethyloxosulfonium chloride with aqueous sodium hydroxide solution.

Also known are dimethylsulfonium methylides of formula (VI) which are furthermore suitable as reactants for carrying out the process variant (β) for the preparation of the oxiranes of the formula (II) ( Heterocycles
8 , 397 (1977)). In the above reaction,
For example, a diluent such as tert. -In the presence of butanol or dimethyl sulfoxide, a strong base such as sodium hydride, sodium amide, sodium methylate, potassium tert. It is also used in the freshly prepared state by preparing it in situ from trimethyloxosulfonium halide or trimethylsulfonium methylsulfate in the presence of butyrate or potassium hydroxide.

Suitable diluents for carrying out the above process for the preparation of the oxiranes of formula (II) are inert organic solvents. The following may preferably be used: alcohols such as tert. Butanol, ethers such as tetrahydrofuran or dioxane, as well as aliphatic and aromatic hydrocarbons such as benzene, toluene or xylene, and strong polar solvents such as dimethyl sulfoxide.

When carrying out the above process for the preparation of the oxiranes of the formula (II), the reaction temperatures can be varied within a considerable range. Generally, this method involves 0 ° C to 1 ° C.
It is carried out at a temperature of 00 ° C, preferably 10 ° C to 60 ° C.

When carrying out the above process for the preparation of oxiranes of the formula (II), 1 to 3 mol of dimethyloxosulfonium methylide of the formula (V) or the formula of the formula (IV) per mol of benzyl ketone of the formula (IV) Dimethylsulfonium methylide of (VI) is commonly used. Formula (I
The oxirane of I) is isolated by conventional methods.
Suitable acid binders for carrying out the method according to the invention are:
All customary inorganic and organic bases. The following can preferably be used: alkali metal carbonates such as sodium and potassium carbonate, also alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, also alkali metal alcoholates such as sodium methylate, sodium. Ethylate, potassium methylate and potassium ethylate and potassium ter
t. Butyrate, and also also lower tertiary alkylamines, cycloalkylamines and aralkylamines, for example triethylamine.

Suitable diluents for carrying out the process according to the invention are all customary inert organic solvents. The following may preferably be used: Nitriles such as acetonitrile, also aromatic hydrocarbons such as benzene, toluene and dichlorobenzene, also formamides such as dimethylformamide, and strongly polar solvents such as dimethylsulfoxide and hexamethylphosphoric acid. Triamide.

When carrying out the process according to the invention, the reaction temperatures can be varied within a considerable range. In general, this method comprises 0 ° C to 200 ° C, preferably 50 ° C to
It is carried out at a temperature of 150 ° C.

When carrying out the process according to the invention, 1 to 4 mol of azole of the formula (III) and 1 to 2 mol of base are preferably used per mol of oxirane of the formula (II). The final product is isolated in the customary manner.

Azolylmethyl-of the formula (I) according to the invention
Fluorocyclopropyl derivatives can be converted into acid addition salts or metal salt complexes.

Suitable acids for the preparation of acid addition salts of the compounds of formula (I) are preferably the acids already mentioned as being the preferred acids in connection with the description of the acid addition salts according to the invention. .

Acid addition salts of compounds of formula (I) can be prepared in a simple manner by conventional salt formation methods, for example by dissolving the compound of formula (I) in a suitable inert solvent and adding an acid such as hydrochloric acid. Can be obtained in a known manner, isolated in a known manner, for example by filtration, and, if appropriate, purified by washing with an inert organic solvent.

Suitable metal salts for the preparation of the metal salt complexes of the compounds of formula (I) have preferably already been mentioned as being the preferred metal salts in connection with the description of the metal salt complexes according to the invention. It is a metal salt.

The metal salt complexes of the compound of formula (I) can be dissolved in a simple manner by conventional methods, for example by dissolving the metal salt in an alcohol such as ethanol and adding this solution to the compound of formula (I). Can be obtained by The metal salt complexes can be isolated in a known manner, for example by filtration, and, if appropriate, purified by recrystallization.

The active compounds according to the invention have a strong microbicidal action and can be used as fungicides.

A fungicidal and fungicidal agent for plant protection is Plasmodiophoresis.
omycetes), oomycetes,
Chitridiomycete
s), Zygomycetes, Ascomycetes, Basidiomycetes
mycetes), and imperfect fungi (Deuterom)
used to control the yeasts).

The following are given by way of example and not by way of limitation of the pathogens of the fungi, fungi and bacterial diseases contained in the above-mentioned general fungi: but not exclusively: Xanthomonas
s) species such as Xanthomonas oryzae (Xantho)
monas oryzae); Pseudomonas (Pse
udomonas species such as Pseudomonas lachryman
s); Erwinia species such as Erwinia amylovo
Ra); Pythium species such as Pythium ultimum; Phytophthora species such as plague (Phyt)
Ophthora infestans; Pseudoperonospora species such as downy mildew (Pseudoperonospora)
humuli or Pseudoperonospor
a cubensis; Plasmopara (Plasmo)
para) species such as downy mildew (Plasmopara v.
iticola); Peronospo
ra) species such as downy mildew (Peronospora pi)
si or P. brassicae); Erishue (E
rysiphe) species, for example (Erysiphe gra
minis); Sphaerotheka
ca) species such as powdery mildew (Sphaerotheca)
fuliginea); Podospera
haera) species such as powdery mildew (Podosphae)
Ra leucotricha); Bench Yulia (Ve
nturia) species such as scab (Venturia i.
naequalis); Pyrenophora (Pyreno-p)
hora) species, such as Pyrenophora
teres or P. graminea) (conidia): Drechslera, synonymous with Helmintho
sporium); Cochliob
olus) species such as leaf spot (Cochliobolus)
sativus) (conidiospore type: Drechsle
ra, synonymous: Helminthosporium); Uromyces species such as rust (Uro)
myces appendiculatus; Puccinia species such as leaf rust (Pucci)
nia recondita); Fungus genus (Till)
etia) species, for example, net lintel smut (Tilleti)
squirrels; Ustilago species, such as Nautilus scab (Ustilago nuda or Ust)
ilago avenae); Periquilaria (Pel)
licularia) species, such as blight (Pellicu)
laria sasakii); Piriquiuraria (Py
ricularia) species such as blast (Pyricu)
laria oryzae); Fusarium
rum) species such as Fusarium krumorum (Fus
arium culmorum); genus Botrytis (Bot)
rytis) species such as Botrytis (Botrytis)
Cinerea); Septoria species, such as blight (Septoria nodorum);
Leptosphaeria species, such as Leptosphaeria nodrum (Leptosphaeria)
eria nodorum); cercospora (Cerc)
ospora) species, such as Cercospora canescens (C
ercospora canescens; Alternaria species such as black spot (Al)
ternaria brassicae; and Pseudocercospore
lla) species, such as Pseudocercosporella
herpotrichoides).

At the concentration required for controlling plant diseases,
Due to the good tolerance of the active compound by plants,
It is possible to treat aboveground parts of plants, growing stems and seeds, and soil.

The active compounds according to the invention are used for controlling rice blast and rice blight on rice and for grain diseases such as Leptosperia nodrum, leaf spot, net blotch, Pseudocercosporella herculae. It is particularly suitable for controlling Potorichoides, Erysihue and Fusarium species. Furthermore, they have a very good action on Bench Yulia, Shuaerotheca and Botrytis.

The substances according to the invention can be used in the usual compositions such as solutions, emulsions, suspensions, powders, encapsulants, coatings, granules, aerosols, polymeric substances for seeds and in coating compositions. It can be converted into fine capsules as well as ULV compositions.

These compositions are prepared in a known manner, for example by extending the active compound with a spreading agent, ie a liquid solvent, a gas and / or solid carrier liquefied under pressure and optionally a surfactant, ie an emulsifier and / or a dispersant and It is manufactured by mixing with a foaming agent. When water is used as the extender, for example, an organic solvent can be used as the auxiliary solvent. As the liquid solvent, mainly aromatic hydrocarbons such as xylene,
Toluene or alkylnaphthalene, chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane, or paraffins such as mineral oil fractions, alcohols such as butanol or glycols and their ethers and esters, Suitable are ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strong polar solvents such as dimethylformamide and dimethylsulfoxide and water; liquefied gas extenders or carriers are
By a liquid which is a gas at ambient temperature and atmospheric pressure is an aerosol propellant base such as butane, propane, nitrogen and carbon dioxide; as a solid carrier, for example ground natural minerals such as kaolin, clay, talc, Chiyoke, quartz, attapulgite, montmorillonite or diatomaceous earth and ground synthetic minerals such as highly dispersed silicic acid, alumina and silicates are suitable; as solid carriers for granules, eg ground and fractionated natural rocks , Eg calcite, marble, pumice, sepiolite and dolomite as well as inorganic and organic ground synthetic granules and granules of organic substances such as sawdust, coconut, corn cobs and tobacco stems; emulsifiers and / or Blowing agents such as nonionic and anionic emulsifiers such as polyoxyethylene Suitable are fatty acid esters, polyoxyethylene fatty alcohol ethers such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulphates, aryl sulphonates and albumin hydrolysis products; dispersants such as lignin sulphite waste liquors and methylcellulose. Are suitable.

Adhesives such as carboxymethylcellulose and powdered, granular or lattice natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate and natural phospholipids such as cephalin and lecithin, and synthetic phospholipids are used in the composition. be able to. Other additives can be mineral and vegetable oils.

Colorants such as inorganic pigments such as iron oxide, titanium oxide and Prussian blue and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes,
And trace amounts of nutrients such as iron, manganese, boron, copper,
Cobalt, molybdenum and zinc salts can be used.

The preparations generally contain from 0.1 to 95 active compounds.
%, Preferably between 0.5 and 90% by weight.

The active compounds according to the invention are other known active compounds such as fungicides, insecticides.
Cides), acaricides and herbicides, and in the form of preparations as a mixture with fertilizers and growth regulators.

The active compounds as such or in the form of their formulations or application forms prepared from said formulations, such as prepared solutions, emulsifiable concentrates, emulsions, powders, suspensions, wettable powders, It can be used in the form of coating agents, soluble powders, powders and granules. This form can be used in the usual way, for example by watering, spraying, atomizing, granulating, dusting, foaming, brushing and the like. Furthermore, the active compounds can be applied by the ultra-low volume method, or by injecting a preparation of the active compound or by injecting the active compound itself into the soil. It is also possible to treat the seeds of the plants.

In use, the application rate of the substances according to the invention can be varied within a substantial range, depending on the nature of the application method. For example, when treating plant parts,
The active compound concentration in the application forms is generally from 1 to 0.0001% by weight, preferably from 0.5 to 0.001.
It is between% by weight. When treating seeds, seed 1 is generally used.
0.001 to 50 g, preferably 0.01 to 1 per Kg
0 g of active compound is required. When treating the soil, generally 0.00001-0.1% by weight at the place of action,
Preferably 0.0001 to 0.02% by weight of active compound is required.

The manufacture and use of the substances according to the invention can be seen from the examples which follow.

Manufacturing Example Example 1

[0060]

[Chemical 25]

5. in 15 ml of dimethylformamide
A solution of 33 g (23.51 mmol) of 2- (2-chlorobenzyl) -2- (1-fluorocyclopropyl) -oxirane was added to 4.87 g (70.54 mmol) of 1 in 20 ml of dimethylformamide. 2,4-triazole and 0.53 g (4.70 mmol) potassium tert. -Add dropwise to the mixture of butyrates at 80 ° C with stirring. When the addition is over, add 80 to the reaction mixture.
Stir at 6 ° C for 6 hours. The solvent is subsequently stripped off under reduced pressure and the remaining residue is taken up in ethyl acetate / water. The aqueous phase is extracted 3 times with ethyl acetate and the combined organic extracts are washed once with water. After drying the organic phase over sodium sulphate and concentration under reduced pressure, the residue is taken up as eluent, ethyl acetate: cyclohexane = 1: 2.
Chromatograph on silica gel using 1: 1. After evaporation of the eluent, 4.3 g (62% of theory) of 1- (2-chlorophenyl) -2- (1-fluorocyclopropyl) -3- (1,2,4-triazol-1-yl). ) -Propan-2-ol is obtained in the form of a solid substance with a melting point of 99-103 ° C.

Preparation of starting materials:

[0063]

[Chemical formula 26]

10.3 ml of 45% strength aqueous sodium hydroxide solution are added to 3.33 g in 30 ml of toluene.
A mixture of (25.86 mmol) trimethylsulfoxonium chloride and 5.0 g (23.51 mmol) 2-chlorobenzyl 1-fluorocyclopropylketone is added dropwise at room temperature over 1 hour. When the addition is over, stirring is continued for 1 hour at room temperature. The reaction mixture is diluted with a little water and the organic phase is separated. The aqueous phase is extracted 3 times with cyclohexane. The combined organic extracts are dried over sodium sulphate and concentrated under reduced pressure. The residue is used for the next reaction without further purification.

[0065]

[Chemical 27]

32.7 g (0.5 mol) of zinc powder, 5
A mixture of 6.4 g (0.35 mol) of 2-chlorobenzyl chloride and 375 ml of dry ethylene glycol dimethyl ether is refluxed for 2 hours under a nitrogen atmosphere.
The reaction mixture is subsequently filtered under nitrogen. The filtrate is 3
6.7 g (0.3 mol) of 1-fluorocyclopropanecarboxylic acid chloride and 21 mg (0.01 mol%) of bis (triphenylphosphine) -palladium (II)
Treat with chloride and reflux under a nitrogen atmosphere for 2 hours. After cooling to room temperature, the reaction mixture is filtered and then concentrated under reduced pressure. Take up the residue in toluene,
The mixture is extracted by shaking with dilute aqueous hydrochloric acid, the organic phase is dried and the solvent is stripped off under reduced pressure.
The remaining residue is subjected to fractional distillation. A gas chromatogram gives 55.4 g of oil consisting of up to 90% 2-chlorobenzyl 1-fluorocyclopropyl ketone. Therefore, the yield is calculated to be 75% of theory.

Preparation of comparative materials of the formula :

[0068]

[Chemical 28]

3. in 10 ml of dimethylformamide
A solution of 3 g (15.7 mmol) of 2- (4-chlorobenzyl) -2- (1-fluorocyclopropyl) -oxirane in 3.20 ml of dimethylformamide.
3 g (47.1 mmol) 1,2,4-triazole and 0.35 g (3.14 mmol) potassium ter
t. -Add dropwise to the mixture of butyrates at 80 ° C with stirring. At the end of the addition, the reaction mixture was heated at 80 ° C for 13
Stir for hours. The solvent is subsequently driven off under reduced pressure and the remaining residue is taken up in water. The aqueous phase is extracted 4 times with dichloromethane. The combined organic phases are dried over sodium sulphate and then concentrated under reduced pressure. The remaining residue is chromatographed on silica gel using the eluent cyclohexane: ethyl acetate = 2: 1. After evaporation of the eluent, 2.2 g (47% of theory) of 1- (4
-Chlorophenyl) -2- (1-fluorocyclopropyl) -3- (1,2,4-triazol-1-yl) -propan-2-ol is obtained in solid form.

¹ H NMR (200 MHz, CDC
l ₃ ): δ = 0.0 to 0.8 (m, 4H); 3.0 (A
B system, 2H); 4.01 (s, 1H, OH);
4.3 (AB system, 2H); 7.28 (s, 4
H); 7.98 (s, 1H); 8.13 (s, 1H).

[0071]

[Chemical 29]

21 ml of 45% strength aqueous sodium hydroxide solution are added to 2.2 g (17.
(1 mmol) trimethylsulfoxonium chloride and 3.3 g (15.5 mmol) 4-chlorobenzyl 1-fluorocyclopropyl ketone are added dropwise over 1 hour at room temperature. When the addition is over, stirring is continued for 2 hours at 40 ° C. The phases are subsequently separated and the aqueous phase is extracted 3 times with toluene. The combined organic phases are washed once with water, dried over sodium sulphate and concentrated under reduced pressure. The residue is used for the next reaction without further purification.

In the use examples which follow, the compounds of the formulas given below were used as comparative substances.

[0074]

[Chemical 30]

Example A Powdery mildew test (barley) / disclosed in EP-OS (European Publication No. 0,297,345) Solvent: 100 parts by weight of dimethylformamide Emulsifier: alkylaryl Polyglycol ether 0.
25 parts by weight To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the abovementioned amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on these plants, powdery mildew (Erysip)
he graminis f. sp. sprinkle on the spores of hordei).

The plants are kept at a temperature of about 20 ° C. and a relative atmospheric humidity of about 8
Put it in the greenhouse at 0% to accelerate the development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, the compound (I-1) according to the present invention was added at 100 ppm at a concentration of 250 ppm in the spray liquid.
% Indicates the degree of effectiveness.

[0079]

[Table 1]

Example B Powdery mildew test (wheat) / protection Solvent: 100 parts by weight of dimethylformamide Emulsifier: alkylaryl polyglycol ether
25 parts by weight To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the abovementioned amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on these plants, powdery mildew (Erysip)
he graminis f. sp. tritici)
Sprinkle with spores.

The plants are kept at a temperature of about 20 ° C. and a relative atmospheric humidity of about 8
Put it in the greenhouse at 0% to accelerate the development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, the compound (I-1) according to the invention was added at 100 ppm at a concentration of 250 ppm in the spray liquor.
% Efficacy degree, while the comparative substance exhibits a 85% efficacy degree.

[0084]

[Table 2]

Example C Powdery mildew test (barley) / treatment Solvent: 100 parts by weight of dimethylformamide Emulsifier: alkylaryl polyglycol ether
25 parts by weight To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the abovementioned amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. Powdery mildew (Erysi) on young plants to test their therapeutic activity.
phe graminis f. sp. holdei)
Sprinkle with spores. 48 hours after inoculation, the plants are sprayed with a preparation of active compound until dew-moist.

The plants are kept at a temperature of about 20 ° C. and a relative atmospheric humidity of about 8
Put it in the greenhouse at 0% to accelerate the development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, the compound (I-1) according to the invention was added at 100 ppm at a concentration of 250 ppm in the spray liquor.
% Indicates the degree of effectiveness.

[0089]

[Table 3]

Example D Powdery mildew test (wheat) / treatment Solvent: 100 parts by weight of dimethylformamide Emulsifier: alkylaryl polyglycol ether
25 parts by weight To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the abovementioned amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. Powdery mildew (Erysi) on young plants to test their therapeutic activity.
phe graminis f. sp. tritic
Sprinkle the spores of i). 48 hours after inoculation, the plants are sprayed with a preparation of active compound until dew-moist.

Plants have a temperature of about 20 ° C. and a relative atmospheric humidity of about 8
Put it in the greenhouse at 0% to accelerate the development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, the compound (I-1) according to the invention was added at 100 ppm at a concentration of 250 ppm in the spray liquor.
% Indicates the degree of effectiveness.

[0094]

[Table 4]

Example E Fusarium nivare (var.maj
us)) test (wheat) / protection solvent: 100 parts by weight of dimethylformamide emulsifier: alkylaryl polyglycol ether
25 parts by weight To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the abovementioned amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating had dried, these plants were given a Fusarium nivale (n
Spray a conidia suspension of ivale (var.majus)).

Plants have a temperature of about 15 ° C. and a relative atmospheric humidity of about 1.
Place in greenhouse at 00% under a transparent culture cover.

Evaluation is carried out 4 days after the inoculation.

In this test, the compound (I-1) according to the invention was added at 100 ppm at a concentration of 250 ppm in the spray liquor.
% Efficacy degree is shown, while the comparative substance shows a 40% efficacy degree.

[0099]

[Table 5]

Example F Nettle spot test (barley) / treatment Solvent: 100 parts by weight of dimethylformamide Emulsifier: alkylaryl polyglycol ether
25 parts by weight To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the abovementioned amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test the therapeutic activity, young plants are sprayed with a conidia suspension of net blotch disease. The plants are kept in the culture room at 20 ° C. and 100% relative atmospheric humidity for 48 hours. These plants are then sprayed with a preparation of the active compound until wet enough to form dew drops. The plants are placed in a greenhouse at a temperature of about 20 ° C. and a relative atmospheric humidity of about 80%.

Evaluation is carried out 7 days after the inoculation.

In this test, the compound (I-1) according to the invention was added at 100 ppm at a concentration of 250 ppm in the spray liquor.
% Indicates the degree of effectiveness.

[0103]

[Table 6]

Example G Leptosphaer
ia nodolum) test (wheat) / protection Solvent: 100 parts by weight of dimethylformamide Emulsifier: alkylaryl polyglycol ether
25 parts by weight To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the abovementioned amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on, these plants are sprayed with a spore suspension of Leptosperia nodrum. These plants are kept in a culture room at 20 ° C. and 100% relative atmospheric humidity for 48 hours.

The plants are placed in a greenhouse at a temperature of about 15 ° C. and a relative atmospheric humidity of about 80%.

Evaluation is carried out 10 days after the inoculation.

In this test, the compound (I-1) according to the invention was added at 100 ppm at a concentration of 250 ppm in the spray liquor.
% Indicates the degree of effectiveness.

[0108]

[Table 7]

Example H Gibberella zeae
Test (barley) / protection Synonyms: Fusarium gramine
arum) Solvent: 100 parts by weight of dimethylformamide Emulsifier: alkylaryl polyglycol ether
25 parts by weight To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the abovementioned amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on, these plants are sprayed with a conidial suspension of Gibberella zeae. The plants are placed in a greenhouse under a transparent culture cover at a temperature of about 20 ° C. and a relative atmospheric humidity of about 100%.

Evaluation is carried out 4 days after the inoculation.

In this test, the compound (I-1) according to the invention was added at 100 ppm at a concentration of 250 ppm in the spray liquor.
% Indicates the degree of effectiveness.

[0112]

[Table 8]

Example I Sclerotinia test (kobito (d)
Warf beans)) / Protection Solvent: Acetone 4.7 parts by weight Emulsifier: Alkylaryl polyglycol ether
3 parts by weight To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the abovementioned amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried, the sclerothiolme (sclerothiolme) scle
Two small pieces of agar covered with growth of R. rotium) are placed on each leaf. The inoculated plants are placed in a darkened, moist chamber at 20 ° C. The size of lesions on these leaves is assessed 3 days after inoculation.

In this test, the compound (I-1) according to the present invention was added at 100 ppm at a concentration of 100 ppm in the spray liquid.
% Indicates the degree of effectiveness.

[0115]

[Table 9]

Example K Powdery mildew test (cucumber) / protection Solvent: 4.7 parts by weight of acetone Emulsifier: Alkylaryl polyglycol ether
3 parts by weight To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the abovementioned amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried, these plants are sprinkled with powdery mildew conidia.

The plants are then placed in a greenhouse at 23-24 ° C. and a relative atmospheric humidity of about 75%.

Evaluation is carried out 10 days after the inoculation.

In this test, the compound (I-1) according to the invention shows a degree of efficacy of 100% at a concentration of 1 ppm in the spray liquor.

[0120]

[Table 10]

Example L Rice blast test (rice) / protection Solvent: Acetone 12.5 parts by weight Emulsifier: Alkylaryl polyglycol ether
3 parts by weight To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the abovementioned amount of solvent and the concentrate is diluted with water and the abovementioned amount of emulsifier to the desired concentration. .

To test for protective activity, young rice plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried on, these plants are inoculated with an aqueous spore suspension of blast. The plants are then placed in a greenhouse at 100% relative atmospheric humidity and 25 ° C.

Evaluation of disease infestation is performed 4 days after inoculation.

In this test, 0.025 in the spray liquor was used.
Compound (I-1) according to the invention used at a concentration of
Shows a degree of efficacy of 80%, while the comparative substance (A) shows no activity.

[0125]

[Table 11]

Example M Pyricularia test (rice) / systemic Solvent: Acetone 12.5 parts by weight Emulsifier: Alkylaryl polyglycol ether
3 parts by weight To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the abovementioned amount of solvent and the concentrate is diluted with water and the abovementioned amount of emulsifier to the desired concentration. .

In order to test the systemic properties, standard soil on which young rice plants are growing is prepared with 40 m of the active compound preparation.
Dispense liquid with l. Seven days after the treatment, the plants are inoculated with an aqueous spore suspension of blast (Pyricularia oryzae). The plants are then evaluated at 25 ° C until evaluated.
At 100 ° C. and 100% relative atmospheric humidity.

Evaluation of disease infestation is performed 4 days after inoculation.

In this test, the compound (I-1) according to the invention shows a degree of efficacy of 100% at an application rate of 100 mg of active compound per 100 cm ² , while the comparative substance (A) shows 50% efficacy. The degree of activity of

[0130]

[Table 12]

Example N Net blotch test (barley) / protection Solvent: 100 parts by weight of dimethylformamide Emulsifier: alkylaryl polyglycol ether
25 parts by weight To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the abovementioned amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. After the spray coating has dried on these plants, net blotch (Pyrenoph)
ora teres).

Next, these plants were treated at 20 ° C. and 100%.
Place in culture chamber for 48 hours at relative atmospheric humidity.

These plants were treated at a temperature of about 20 ° C. and about 80
Place in greenhouse at relative atmospheric humidity of%. Evaluation is carried out 7 days after the inoculation.

In this test, the compound (I-1) according to the invention shows a degree of activity of more than 80% at an active compound concentration of 250 ppm in the spray liquor, whereas the comparative substance (A) has a degree of 25%. Indicates.

[0135]

[Table 13]

Example O Fusarium nivale test (wheat) / protection In order to produce suitable preparations of active compound, sprayable, commercially available active compound preparations are in each case prepared. Dilute with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound until wet with dew drops. After the spray coating had dried, the plants were given Fusarium nivale.
var. The conidia suspension of Nivale) is sprayed on.

Plants have a temperature of about 15 ° C. and a relative atmospheric humidity of about 1
Place in a greenhouse in a translucent culture room at 00%.

Evaluation is carried out 4 days after the inoculation.

In this test, the compound (I-1) according to the invention shows a degree of activity of 90% at a concentration of 250 ppm of active compound in the spray liquor, while the comparative substance (A)
Indicates the degree of activity of 30%.

[0141]

[Table 14]

The main features and aspects of the present invention are as follows.

1) Expression

[0144]

[Chemical 31]

[Wherein R is

[0146]

[Chemical 32]

Of the azolylmethyl-fluorocyclopropyl derivative and acid addition salts and metal salt complexes thereof.

2) Expression

[0149]

[Chemical 33]

[Wherein R is

[0151]

[Chemical 34]

A method for the preparation of azolylmethyl-fluorocyclopropyl derivatives of and the acid addition salts and metal salt complexes thereof

[0153]

[Chemical 35]

[Wherein, R has the meaning described above]
Oxirane of the formula, if appropriate in the presence of an acid binder and in the presence of a diluent.

[0155]

[Chemical 36]

By reacting with 1,2,4-triazole
And, if appropriate, the subsequent addition of an acid or metal salt onto the compound of formula (I) produced.

3) At least one azolylmethyl-fluorocyclopropyl derivative of the formula (I) described above or an acid addition salt or metal salt complex of the azolylmethyl-fluorocyclopropyl derivative of the formula (I). A sterilizing and fungicidal composition.

4) Use of the azolylmethyl-fluorocyclopropyl derivative of the formula (I) or the acid addition salt thereof and metal salt complex thereof as described in 1 above for controlling fungi.

5) The azolylmethyl-fluorocyclopropyl derivative of the formula (I) or the acid addition salt or metal salt complex thereof described in 1 above is applied to fungi / mold and / or their environment. How to control fungi and mold.

6) Sterilization, characterized in that the azolylmethyl-fluorocyclopropyl derivative of formula (I) or the metal salt complex or acid addition salt thereof described in 1 above is mixed with a carrier and / or a surface-active substance. Method for the production of fungicides.

Equation 7)

[0162]

[Chemical 37]

[Wherein R is

[0164]

[Chemical 38]

Represents an oxirane.

Equation 8)

[0167]

[Chemical Formula 39]

[In the formula, R is

[0169]

[Chemical 40]

A method for the preparation of an oxirane of

[0171]

[Chemical 41]

[Wherein R has the above-mentioned meaning]
Benzyl ketone of α) formula in the presence of a diluent

[0173]

[Chemical 42]

Dimethyloxosulfonium methylide of
Or β) formula

[0175]

[Chemical 43]

A method characterized by reacting with either of the dimethylsulfonium methylides of.

Front page continuation (72) Inventor Siuteh Juan Beem Germany Day 5000 Cologne 80 Andreas-Grihuius-Syutrase 9 (72) Inventor Hermann Hagemann Federal Republic of Germany Day 5090 Lef Erkusen 1-Kandeinski-Syutrase 52 (72) Inventor Claus Syutrech, Federal Republic of Germany Day 5650 Solingen 19, Rollsberger Schutlerse 22 (72) Inventor Siutte Juan Doutsman, Federal Republic of Germany Day 4010 Hilden 1, Kosenberg 10 (72) Inventor Heinz-Bilhelm Dene Germany Day 4019 Monheim Krischaischetraße 81 (72) Inventor Gerd Hensler Germany Day 5090 Lef Erkusen 3 Am Allenzberg 58

Claims (6)

[Claims] 1. The formula: [In the formula, R is The azolylmethyl-fluorocyclopropyl derivative and the acid addition salts and metal salt complexes thereof. 2. The formula: [In the formula, R is For the preparation of azolylmethyl-fluorocyclopropyl derivatives of and the acid addition salts and metal salt complexes thereof of the formula An oxirane of the formula where R has the meanings given above, if appropriate in the presence of an acid binder and in the presence of a diluent. Of 1,2,4-triazole, and if appropriate, subsequent addition of an acid or metal salt onto the compound of formula (I) formed. 3. At least one azolylmethyl-fluorocyclopropyl derivative of formula (I) or an acid addition salt or metal salt complex of an azolylmethyl-fluorocyclopropyl derivative of formula (I). A sterilizing and fungicidal composition. 4. The method according to claim 1, wherein the azolylmethyl-fluorocyclopropyl derivative of the formula (I) or an acid addition salt or metal salt complex thereof is applied to fungi / mold and / or their environment. How to control fungi and mold. 5. The formula: [In the formula, R is Represents] oxirane. 6. The formula: [In the formula, R is For the preparation of an oxirane of the formula: A benzyl ketone of the formula where R has the meanings given above and α) in the presence of a diluent Dimethyloxosulfonium methylide of, or β) formula: The method characterized by reacting with either dimethyl sulfonium methylide.